CN106276824B - A method of high nitrogen vanadium nitride is prepared with coke - Google Patents
A method of high nitrogen vanadium nitride is prepared with coke Download PDFInfo
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- CN106276824B CN106276824B CN201610598995.5A CN201610598995A CN106276824B CN 106276824 B CN106276824 B CN 106276824B CN 201610598995 A CN201610598995 A CN 201610598995A CN 106276824 B CN106276824 B CN 106276824B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/0617—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with vanadium, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
The present invention provides a kind of methods preparing high nitrogen vanadium nitride with coke, the described method comprises the following steps：Raw material vanadium trioxide, graphite, coke and water are subjected to mixed pelletizing and are dried to obtain pelletizing, wherein the mass ratio of graphite and coke is 1:(0.05~0.2)；Pelletizing after drying is fired in a nitrogen atmosphere, is 1450~1500 DEG C in the central temperature of nitridation section, nitrogen flow is maintained at 100~350m3Under conditions of/h vanadium nitride finished product is generated by reduction and nitridation.The present invention substitutes the preparation that part graphite carries out high nitrogen vanadium nitride with coke, using contained by ash content in coke simple substance silica and fe participate in reaction, by the synergistic effect of silica, fe and carbon, the high nitrogen vanadium nitride of nitrogen content >=16wt% is prepared；Meanwhile the method reduces graphite dosage, reduces cost.
Description
Technical field
The invention belongs to vanadium alloy technical fields, are related to a kind of method preparing high nitrogen vanadium nitride with coke, more particularly to
A method of graphite is substituted with coke fraction and prepares high nitrogen vanadium nitride.
Background technology
Vanadium is added in low-alloy steel and mainly plays precipitation enhancement.And nitrogen pick-up can improve the lasting strong of steel in steel
Degree, improves the toughness and plasticity of steel, while can also improve the heat resistanceheat resistant intensity of steel and anti-short creep ability.Often increase in vanadium steel
6MPa just can be improved in the intensity of the nitrogen of 10ppm, steel, this is because after nitrogen content increase, promotes vanadium from solid solution condition to V (CN)
The transfer of precipitated phase.Precipitate size reduces while V (CN) is largely formed and is precipitated.Solid solution V amount of precipitations are greatly decreased, into one
Step increases the stability of austenite, reduces phase transition temperature, V (CN) precipitated phase of a large amount of small and disperseds makes the reinforcing effect of steel
It is obviously improved.The production of high nitrogen vanadium nitride product, it is possible to provide a large amount of nitrogen makes the invigoration effect of vanadium give full play to.It is not reducing
Vanadium nitride dosage can be reduced on the basis of steel strength, to reduce steel-making cost.
So-called high nitrogen vanadium nitride refers to the vanadium nitride that nitrogen content is more than 16%, according to VN alloy standard GB/T/T
20567-2006 provides that VN alloy is divided to VN12 and two trades mark of VN16, in wherein VN12 V be 77~81%, N be 10~
14%, C≤10%, P≤0.06%, S≤0.1%；It is 14~18%, C≤6% that V, which is 77~81%, N, in VN16, P≤
0.06%, S≤0.1%.
It produces vanadium nitride and generally uses graphite, vanadium trioxide and binder dispensing in proportion, ball is pressed into after mixing, through drying
After dry and screening, it is added in the High-temp. kiln under nitrogen atmosphere protection, temperature is under conditions of 0~1500 DEG C, nitrogen flow
It is maintained at 100~350m3/ h obtains VN alloy after reduction and nitridation.Match carbon when the method produces in raw material proportioning
Amount generally needs excessive 15%.
Reaction formula in aforementioned production method is：
V2O3(s)+3C(s)+N2(g)=2VN (s)+3CO (g)
CN 1422800 discloses a kind of production method of vanadium nitride, and the method is by barium oxide, graphite and 2% poly- second
After enol is uniformly mixed pressure ball, it is added in the pushed bat kiln or tunnel oven for being connected with protection and reaction gas (nitrogen and/or ammonia),
2~6h is reacted at a temperature of 1000~1800 DEG C, is discharged after being subsequently cooled to 100~250 DEG C.But this method only discloses nitridation
The raw material composition of vanadium and broad reaction temperature and reaction time.And used reacting furnace is horizontal positioned push plate
The ingredient of kiln or tunnel oven, obtained product is 77~81%V and 1~8%N.
CN 102173395A disclose a kind of easy vanadium nitride production method, and the method is by V2O5Powder and graphite powder are pressed
4:1 weight ratio be sufficiently mixed on dry-mixed machine after by 100:The polyvinyl alcohol water solution that content is 4% is added in 15 weight ratio,
Through mixing, pressure ball and drying, the mixing sphere of powder layering after drying is packed into truck, enters stove and sealing fire door, is led under vacuum condition
After entering nitrogen, after 800 DEG C, 1350 DEG C and 1600 DEG C keep 5h, 6h and the total 20h of 6~10h respectively, power failure is cooled to 150 DEG C and goes out
Stove.It is described to disclose accurate raw material proportioning and reaction time and reaction temperature, but the consumption proportion of its graphite powder is far low
Influence of the nitrogen to reaction is not announced in normal reaction demand and, and its production process is completion and reaction used at times
Stove is vacuum drying oven.It is 77.42%V and 15.63%N that it, which produces the ingredient of product,.
It can be seen that vanadium nitride production at present there are mainly two types of method, i.e. high-temperature vacuum is prepared and the antivacuum preparation of high temperature.
But the above method mainly produces low nitrogen vanadium nitride, and the technology that can be used for high nitrogen vanadium nitride production is seldom.
Invention content
For the problems of in the prior art, the present invention provides a kind of sides preparing high nitrogen vanadium nitride with coke
Method.The method substitutes the preparation that part graphite carries out high nitrogen vanadium nitride with coke, utilizes the simple substance two contained by ash content in coke
Silica and fe participate in reaction, by the synergistic effect of silica, fe and carbon, prepare nitrogen content >=
The high nitrogen vanadium nitride of 16wt%；Meanwhile the method reduces graphite dosage, reduces cost.
For this purpose, the present invention uses following technical scheme：
The present invention provides a kind of methods preparing high nitrogen vanadium nitride with coke, the described method comprises the following steps：
(1) raw material vanadium trioxide, graphite, coke and water are subjected to mixed pelletizing and are dried to obtain pelletizing, wherein graphite
Mass ratio with coke is 1:(0.05~0.2)；
(2) pelletizing after drying is fired in a nitrogen atmosphere, vanadium nitride is made.
Wherein, the mass ratio of graphite and coke can be 1:0.05、1:0.07、1:0.1、1:0.13、1:0.15、1:0.17 or
1:0.2 etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize the technical purpose and advantageous effect of the present invention.
As currently preferred technical solution, the dosage of step (1) described vanadium trioxide is the 70 of raw material gross mass
~80wt%, such as 70wt%, 72wt%, 74wt%, 76wt%, 78wt% or 80wt% etc., it is not limited to cited
Numerical value, other numerical value are feasible in listed range, further preferably 74~75wt%.
Preferably, in step (1) water dosage be raw material gross mass 8~12wt%, such as 8wt%, 9wt%,
10wt%, 11wt% or 12wt% etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible, into
One step is preferably 9~10%.
Preferably, the mass ratio of graphite and coke described in step (1) is 1:0.1.
Preferably, the total amount of graphite and coke described in step (1) accounts for 15~20wt% of whole raw material gross masses, such as
15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt% etc., further preferably 20wt%.
As currently preferred technical solution, content of ashes is 12~13.5wt%, example in coke described in step (1)
Such as 12wt%, 12.3wt%, 12.5wt%, 12.7wt%, 13wt%, 13.3wt% or 13.5wt%, it is not limited to
Cited numerical value, other interior numerical value of listed range are feasible.
Preferably, in the ash content silica content >=55wt%, such as 55wt%, 57wt%, 60wt%,
63wt%, 65wt%, 67wt%, 70wt% or 73wt% etc. and the above numerical value, it is not limited to cited numerical value, institute
Other numerical value are feasible within the scope of row.
Preferably, in the ash content iron content be 0.5~1wt%, such as 0.5wt%, 0.6wt%, 0.7wt%,
0.8wt%, 0.9wt% or 1wt% etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible, into
One step is preferably 1wt%.
In the present invention, the usage ratio of coke and graphite forms decision by coke.The content of ash content is about in the coke
For 12~13.5wt%, and in ash content silica content >=55wt%, while the also fe containing 0.5~1wt%.
It prepares during vanadium nitride during carbon reduction reaction, silica can synthesize nitridation under 1400~1450 DEG C of nitrogen atmosphere
Silicon, reaction are as follows：
3SiO2(s)+6C(s)+2N2(g)→Si3N4(s)+6CO(g)
SiO2(s)+C(s)→SiO(g)+CO(g)
3SiO(g)+2N2(g)+3CO(g)→Si3N4(s)+3CO2(g) or,
3SiO(g)+2N2(g)+3C(s)→Si3N4(s)+3CO(g)
In reaction process, the nitrogen content of the silicon nitride of generation is about 38~39wt%；And the iron in ash content is burnt in vanadium nitride
Can be used as additive in system can promote the nitridation of vanadium.Therefore, it using the synergistic effect of silica, fe and carbon, can be improved
Nitrogen content in product vanadium nitride.
Simultaneously as coke ratio graphite specific surface area is small, participating in reaction will slowly, therefore the ash content of coke is more, silica
It is more with iron, the content of nitrogen can be more preferably improved, but will also result in the reduction of vanadium in vanadium nitride simultaneously.And vanadium nitride standard pair
Vanadium has minimum requirements, therefore the addition of STRENGTH ON COKE needs to carry out stringent control, and the present invention is obtained by numerous studies, works as stone
The mass ratio of ink and coke is 1:When (0.05~0.2), the content for ensureing vanadium while improving nitrogen content can be reached, and with stone
The mass ratio of ink and coke is 1:Effect is optimal when 0.10.
In addition, the nitridation reaction that also should ensure that in sintering procedure in the sintering procedure of vanadium nitride, i.e. control reaction item
Nitrogen partial pressure, reaction temperature and reaction time in part, including kiln around material etc..
As currently preferred technical solution, the flow of stream of nitrogen gas described in step (2) is 100~350m3/ h, example
Such as 100m3/h、130m3/h、150m3/h、170m3/h、200m3/h、230m3/h、250m3/h、270m3/h、300m3/h、330m3/
H or 350m3/ h etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible, further preferably
200~300m3/h.
In this hair, the nitrogen flow is one of the key factor in vanadium nitride preparation process, needs to control in preparation process
Nitrogen flow processed in the reasonable scope, to control the nitrogen partial pressure in kiln around material, ensures the progress of nitridation reaction, if nitrogen
Flow is too low, and nitridation can be made insufficient；If nitrogen flow is excessively high, temperature declines soon, increases power heating, causes to waste, reduces
The service life of kiln.
As currently preferred technical solution, sintering procedure carries out in pushed bat kiln described in step (2).
As currently preferred technical solution, sintering procedure described in step (2) includes preheating section, carbon reduction section, nitrogen
Change section and cooling section.
As currently preferred technical solution, the temperature of the preheating section is 200~600 DEG C, for example, 200 DEG C, 250
DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C or 600 DEG C etc., it is not limited to cited numerical value, institute
Other numerical value are feasible within the scope of row, further preferably 400~600 DEG C.
Preferably, the temperature of the carbon reduction section be 600~1100 DEG C, such as 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C,
1000 DEG C or 1100 DEG C etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible, further preferably
It is 800~1000 DEG C.
Preferably, it is described nitridation section temperature be 1100~1500 DEG C, such as 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250
DEG C, 1300 DEG C, 1350 DEG C, 1400 DEG C or 1500 DEG C etc., it is not limited to cited numerical value, other numerical value in listed range
It is feasible, further preferably 1250~1500 DEG C.
Preferably, the upper temp of the cooling section be 800~1000 DEG C such as 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or
1000 DEG C etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible, further preferably 800~
900℃。
Preferably, the temperature of lower of the cooling section be≤200 DEG C, such as 200 DEG C, 190 DEG C, 180 DEG C, 170 DEG C, 160
DEG C, 150 DEG C, 140 DEG C, 130 DEG C, 120 DEG C, 110 DEG C or 100 DEG C etc. and lower temperature, it is not limited to cited number
Value, other numerical value are feasible in listed range, further preferably≤150 DEG C.
In present invention, it is desirable to it is 800~1000 DEG C to keep cooling section upper temp, temperature of lower is≤200 DEG C.Due to nitrogen
The nitridation process for changing vanadium is exothermic reaction, reduces nitriding temperature in the case that nitrogen content is higher, although reducing nitridation reaction speed
It spends but nitridation process can be promoted, further increase product nitrogen content；Vanadium nitride can be aoxidized when more than 200 DEG C, therefore be defined
Cooling section temperature of lower is less than 200 DEG C, and product is avoided to aoxidize.
As currently preferred technical solution, the central temperature of the nitridation section is 1450~1500 DEG C, such as 1450
DEG C, 1460 DEG C, 1470 DEG C, 1480 DEG C, 1490 DEG C or 1500 DEG C etc., it is not limited to cited numerical value, in listed range
Other numerical value are feasible.
In the present invention, the central temperature of the nitridation section need to be maintained at 1450~1500 DEG C, to ensure the complete of nitridation reaction
It is complete to carry out, and then improve the nitrogen content of product.
Preferably, the raw material nitridation section residence time be 16~30h, such as 16h, 18h, 20h, 22h, for 24 hours,
26h, 28h or 30h etc., it is not limited to cited numerical value, other interior numerical value of listed range are feasible, further preferably
16~20h.
In the present invention, the raw material extends 0.5~2h in the residence time of bringing-up section compared with prior art, it is therefore intended that makes nitrogen
The reaction was complete for change.
As currently preferred technical solution, nitrogen content >=16wt% in vanadium nitride made from step (2).
As currently preferred technical solution, the described method comprises the following steps：
(1) raw material vanadium trioxide, graphite, coke and water are subjected to mixed pelletizing and are dried to obtain pelletizing, wherein three oxygen
The dosage for changing two vanadium is 74~75wt% of raw material gross mass, and the dosage of water is 9~10wt% of raw material gross mass, graphite and coke
The mass ratio of charcoal is 1:0.15, the total amount of graphite and coke accounts for the 20wt% of whole raw material gross masses, and content of ashes is in coke
12~13.5wt%, content >=55wt% of silica in ash content, the content of iron is 1wt% in ash content；
(2) it is 200~300m in flow by the pelletizing after drying3It is carried out in feeding pushed bat kiln successively under the nitrogen atmosphere of/h
Preheated section, carbon reduction section, nitridation section and cooling section are fired, wherein the temperature of carbon reduction section is 800~1000 DEG C, nitrogen
The temperature for changing section is 1250~1500 DEG C, and the central temperature for nitrogenizing section is 1450~1500 DEG C, and the upper temp of cooling section is 800
~900 DEG C, the temperature of lower of cooling section is≤150 DEG C, and raw material is 16~20h in the residence time of nitridation section, and nitrogen content is made
The vanadium nitride of >=16wt%.
Compared with prior art, the invention has the advantages that：
(1) the method for the invention substitutes part graphite with coke and utilizes two by adjusting the proportioning between raw material components
The synergistic effect of silica, fe and carbon produces vanadium nitride with pushed bat kiln, and by controlling nitrogen flow and nitridation reaction
Temperature and time, to ensure that nitrogen and reduction generate stabilization and uniformly circulation of the gas in kiln in stove, can be such that product fires steady
It is fixed, and then the high nitrogen vanadium nitride product of nitrogen content >=16wt% is made；Meanwhile graphite is substituted with coke, reduce the use of graphite
Amount, reduces cost.
(2) the heating highest warm area of nitridation reaction of the present invention is maintained at 1450~1500 DEG C, and the reaction time is than former work
Skill extends 0.5~2 hour, it is ensured that nitridation is complete, further increases product nitrogen content.
(3) the high nitrogen vanadium nitride that the present invention produces, product nitrogen content is far above original formulation product nitrogen content, in its conduct
When steel-making additive, the increase of nitrogen makes vanadium strengthen effect and be not fully exerted, and so that the performance of product is promoted, and then bring
The raising of product price and product competitiveness in the market.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only the simple example of the present invention, does not represent or limit the scope of the present invention, this
Invention protection domain is subject to claims.
The present invention provides a kind of methods preparing high nitrogen vanadium nitride with coke, the described method comprises the following steps：
(1) raw material vanadium trioxide, graphite, coke and water are subjected to mixed pelletizing and are dried to obtain pelletizing, wherein graphite
Mass ratio with coke is 1:(0.05~0.2)；
(2) pelletizing after drying is fired in a nitrogen atmosphere, vanadium nitride is made.
Typical but non-limiting embodiment of the invention is as follows：
Embodiment 1：
Present embodiments provide it is a kind of 5wt% graphite substituted with coke prepare the production method of vanadium nitride, in the coke
Content of ashes is 12~13.5wt%, content >=55wt% of silica in ash content, and the content of iron is 1wt% in ash content；
It the described method comprises the following steps：
Raw material 1000kg vanadium trioxides, 247kg graphite, 13kg coke and 99.2kg water are put into batch mixer after mixing
Pressure ball, green pellets are fired after dry sieve in input pushed bat kiln, and the flow that stream of nitrogen gas is controlled in sintering procedure is
200m3The temperature of/h, carbon reduction section are 800 DEG C, and the central temperature for nitrogenizing section is 1450 DEG C, and the upper temp of cooling section is 900
DEG C, the temperature of lower of cooling section is≤150 DEG C, and raw material is 20h in the residence time of nitridation section, and vanadium nitride product is made.
Comparative example 1：
This comparative example provides a kind of production method of vanadium nitride, in the method other than raw material does not add coke,
His material amounts and preparation process are in the same manner as in Example 1, and vanadium nitride product is made.
Embodiment 2：
Present embodiments provide it is a kind of 10wt% graphite substituted with coke prepare the production method of vanadium nitride, in the coke
Content of ashes is 12~13.5wt%, content >=55wt% of silica in ash content, and the content of iron is 1wt% in ash content；
It the described method comprises the following steps：
Raw material 1000kg vanadium trioxides, 234kg graphite, 26kg coke and 99.2kg water are put into batch mixer after mixing
Pressure ball, green pellets are fired after dry sieve in input pushed bat kiln, and the flow that stream of nitrogen gas is controlled in sintering procedure is
200m3The temperature of/h, carbon reduction section are 800 DEG C, and the central temperature for nitrogenizing section is 1450 DEG C, and the upper temp of cooling section is 800
DEG C, the temperature of lower of cooling section is≤150 DEG C, and raw material is 16h in the residence time of nitridation section, and vanadium nitride product is made.
Comparative example 2：
This comparative example provides a kind of production method of vanadium nitride, in the method other than raw material does not add coke,
His material amounts and preparation process are in the same manner as in Example 1, and vanadium nitride product is made.
Embodiment 3：
Present embodiments provide it is a kind of 15wt% graphite substituted with coke prepare the production method of vanadium nitride, in the coke
Content of ashes is 12~13.5wt%, content >=55wt% of silica in ash content, and the content of iron is 1wt% in ash content；
It the described method comprises the following steps：
Raw material 1000kg vanadium trioxides, 221kg graphite, 39kg coke and 99.2kg water are put into batch mixer after mixing
Pressure ball, green pellets are fired after dry sieve in input pushed bat kiln, and the flow that stream of nitrogen gas is controlled in sintering procedure is
350m3The temperature of/h, carbon reduction section are 1100 DEG C, and the central temperature for nitrogenizing section is 1500 DEG C, and the upper temp of cooling section is 900
DEG C, the temperature of lower of cooling section is≤150 DEG C, and raw material is 20h in the residence time of nitridation section, and vanadium nitride product is made.
Comparative example 3：
This comparative example provides a kind of production method of vanadium nitride, in the method other than raw material does not add coke,
His material amounts and preparation process are in the same manner as in Example 1, and vanadium nitride product is made.
Embodiment 4：
Present embodiments provide it is a kind of 20wt% graphite substituted with coke prepare the production method of vanadium nitride, in the coke
Content of ashes is 12~13.5wt%, content >=55wt% of silica in ash content, and the content of iron is 1wt% in ash content；
It the described method comprises the following steps：
Raw material 1000kg vanadium trioxides, 204kg graphite, 52kg coke and 99.2kg water are put into batch mixer after mixing
Pressure ball, green pellets are fired after dry sieve in input pushed bat kiln, and the flow that stream of nitrogen gas is controlled in sintering procedure is
200m3The temperature of/h, carbon reduction section are 1000 DEG C, and the central temperature for nitrogenizing section is 1450 DEG C, and the upper temp of cooling section is 900
DEG C, the temperature of lower of cooling section is≤150 DEG C, and raw material is 20h in the residence time of nitridation section, and vanadium nitride product is made.
Comparative example 4：
This comparative example provides a kind of production method of vanadium nitride, in the method other than raw material does not add coke,
His material amounts and preparation process are in the same manner as in Example 1, and vanadium nitride product is made.
Comparative example 5：
This comparative example provides a kind of production method of vanadium nitride, in addition to the mass ratio of graphite and coke is in the method
1:Outside, unclassified stores dosage and preparation process are in the same manner as in Example 1 for 0.3 (i.e. graphite of the coke instead of 30wt%), system
Obtain vanadium nitride product.
If the dosage that can be seen that graphite and coke from the result of comparative example 5 has been more than required proportioning, can cause in product
The reduction of content of vanadium, and then vanadium nitride product is made to cannot be satisfied national standard.
Comparative example 6：
This comparative example provides a kind of production method of vanadium nitride, in addition to the flow of stream of nitrogen gas is in the method
50m3/ h (＜ 100m3/ h) outside, unclassified stores dosage and preparation process are in the same manner as in Example 1, and vanadium nitride product is made.
To be prepared in 1-4 of the embodiment of the present invention and comparative example 1-7 each group in vanadium nitride product be grouped as and content into
Row test, test result are as shown in table 1.
Table 1：The composition content table of vanadium nitride product in embodiment 1-4 and comparative example 1-7
Integrated embodiment 1-4 and comparative example 1-6 can be seen that the method for the invention and substitute part graphite with coke, lead to
The proportioning between adjustment raw material components is crossed, using the synergistic effect of silica, fe and carbon, is produced and is nitrogenized with pushed bat kiln
Vanadium, and by controlling nitrogen flow and nitridation reaction temperature and time, to ensure that nitrogen and reduction generate gas in kiln in stove
Interior stabilization and uniformly circulation, can make product fire the high nitrogen vanadium nitride product stablized, and then nitrogen content >=16wt% is made；Together
When, graphite is substituted with coke, reduces the dosage of graphite, reduces cost.
Meanwhile the heating highest warm area of nitridation reaction of the present invention is maintained at 1400~1500 DEG C, the reaction time is than former
Prolonged process 0.5~2 hour, it is ensured that nitridation is complete, further increases product nitrogen content.
Also, the high nitrogen vanadium nitride that the present invention produces, product nitrogen content are far above original formulation product nitrogen content, in its work
For steel-making additive when, the increase of nitrogen makes vanadium strengthen effect and be not fully exerted, and so that the performance of product is promoted, and then band
Carry out the raising of product price and product competitiveness in the market.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (28)
1. a kind of method preparing high nitrogen vanadium nitride with coke, which is characterized in that the described method comprises the following steps：
(1) raw material vanadium trioxide, graphite, coke and water are subjected to mixed pelletizing and are dried to obtain pelletizing, wherein graphite and coke
The mass ratio of charcoal is 1:(0.05~0.2), content of ashes is 12~13.5wt% in the coke, and silica contains in ash content
Amount >=55wt%, the content of iron is 0.5~1wt% in ash content；
(2) pelletizing after drying is fired in a nitrogen atmosphere, vanadium nitride is made.
2. according to the method described in claim 1, it is characterized in that, the dosage of step (1) described vanadium trioxide is that raw material is total
70~80wt% of quality.
3. according to the method described in claim 2, it is characterized in that, the dosage of step (1) described vanadium trioxide is that raw material is total
74~75wt% of quality.
4. according to the method described in claim 1, it is characterized in that, in step (1) water dosage be raw material gross mass 8~
12wt%.
5. according to the method described in claim 4, it is characterized in that, in step (1) water dosage be raw material gross mass 9~
10wt%.
6. according to the method described in claim 1, it is characterized in that, the mass ratio of graphite and coke described in step (1) is 1:
0.1。
7. according to the method described in claim 1, it is characterized in that, the total amount of graphite and coke described in step (1) accounts for whole
15~20wt% of raw material gross mass.
8. the method according to the description of claim 7 is characterized in that the total amount of graphite and coke described in step (1) accounts for whole
The 20wt% of raw material gross mass.
9. according to the method described in claim 1, it is characterized in that, the content of iron is 1wt% in ash content described in step (1).
10. according to the method described in claim 1, it is characterized in that, the flow of stream of nitrogen gas described in step (2) be 100~
350m3/h。
11. according to the method described in claim 10, it is characterized in that, the flow of stream of nitrogen gas described in step (2) be 200~
300m3/h。
12. according to the method described in claim 1, it is characterized in that, sintering procedure described in step (2) in pushed bat kiln into
Row.
13. according to the method described in claim 1, it is characterized in that, sintering procedure described in step (2) includes preheating section, carbon
Reduction section, nitridation section and cooling section.
14. according to the method for claim 13, which is characterized in that the temperature of the preheating section is 200~600 DEG C.
15. according to the method for claim 14, which is characterized in that the temperature of the preheating section is 400~600 DEG C.
16. according to the method for claim 13, which is characterized in that the temperature of the carbon reduction section is 600~1100 DEG C.
17. according to the method for claim 16, which is characterized in that the temperature of the carbon reduction section is 800~1000 DEG C.
18. according to the method for claim 13, which is characterized in that the temperature of the nitridation section is 1100~1500 DEG C.
19. according to the method for claim 18, which is characterized in that the temperature of the nitridation section is 1250~1500 DEG C.
20. according to the method for claim 13, which is characterized in that the upper temp of the cooling section is 800~1000 DEG C.
21. according to the method for claim 20, which is characterized in that the upper temp of the cooling section is 800~900 DEG C.
22. according to the method for claim 13, which is characterized in that the temperature of lower of the cooling section is≤200 DEG C.
23. according to the method for claim 22, which is characterized in that the temperature of lower of the cooling section is≤150 DEG C.
24. according to the method for claim 13, which is characterized in that the central temperature of the nitridation section is 1450~1500
℃。
25. according to the method for claim 13, which is characterized in that the raw material nitridation section residence time be 16~
30h。
26. according to the method for claim 25, which is characterized in that the raw material nitridation section residence time be 16~
20h。
27. according to the method described in claim 1, it is characterized in that, nitrogen content in vanadium nitride made from step (2) >=
16wt%.
28. according to the method described in claim 1, it is characterized in that, the described method comprises the following steps：
(1) raw material vanadium trioxide, graphite, coke and water are subjected to mixed pelletizing and are dried to obtain pelletizing, wherein three oxidations two
The dosage of vanadium is 74~75wt% of raw material gross mass, and the dosage of water is 9~10wt% of raw material gross mass, graphite and coke
Mass ratio is 1:0.1, the total amount of graphite and coke accounts for the 20wt% of whole raw material gross masses, in coke content of ashes be 12~
13.5wt%, content >=55wt% of silica in ash content, the content of iron is 1wt% in ash content；
(2) it is 200~300m in flow by the pelletizing after drying3It carries out passing through successively in feeding pushed bat kiln under the nitrogen atmosphere of/h pre-
Hot arc, carbon reduction section, nitridation section and cooling section are fired, wherein the temperature of carbon reduction section is 800~1000 DEG C, nitrogenizes section
Temperature be 1250~1500 DEG C, the central temperature for nitrogenizing section is 1450~1500 DEG C, the upper temp of cooling section is 800~
900 DEG C, the temperature of lower of cooling section is≤150 DEG C, and raw material is 16~20h in the residence time of nitridation section, obtained nitrogen content >=
The vanadium nitride of 16wt%.
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